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MALDI-TOF MS was used to study the end-group distribution of a series of poly(m-phenyleneisophthalamide) oligomers which were synthesized using various mole percent ratios of diamine to diacid chloride (90:10, 80:20, 70:30, 60:40, 50:50, 40:60, 30:70, 20:80, and 10:90) to clarify results obtained in previous work published in this journal. Oligomers synthesized with excess diamine or excess diacid chloride were found to contain abundances of amine or carboxylate end groups, respectively, as expected. Oligomers synthesized with equal molar ratios of reactants produced cyclic species which were also found in a previous publication as an oligomer in commercially produced, high molecular mass Nomex.

Multiwalled nanotubes (MWNTs) and single-wall carbon nanotubes (SWNTs) with covalently linked porphyrin antennae were synthesized and characterized as potential supramolecular donor-acceptor complexes. The absorption and fluorescence of these complexes show that the carbon nanotubes serve as an efficient electron acceptor and pave the way to construct novel photovoltaic devices and light-harvesting systems using various porphyrin-functionalized carbon nanotubes.

Poly(L-lactide)-block-poly(ethylene oxide)-block-poly(L-lactide) triblock copolymers (PLLA-b-PEO-b-PLLA) were fractionated in terms of the number of LLA units by liquid chromatography at the critical condition (LCCC) of PEO block. The fractionated samples were identified using MALDI-TOF mass spectrometry. The dependence of the LCCC retention of the diblock and triblock copolymers on the degree of polymerization of PLLA block(s) follows Martin's rule very well. Unlike the case of PEO-b-PLLA diblock copolymer reported earlier (Lee, H.; et al. Macromolecules 1999, 32, 4143), however, a splitting of the elution peaks containing the same number of LLA units was found. The peak splitting was ascribed to the different length distributions of PLLA blocks at the two ends of the PEO block. From the relative intensities of the peaks, the split peaks were assigned to different isomeric structures of the PLLA blocks. From these results we conclude that the interaction of the triblock copolymers with the stationary phase is affected by the distribution of the interacting blocks at the two ends of the center PEO block, in addition to the total number of LLA units in the triblock copolymer.

Presents the characterization of poly(L-lactide)-block-poly-(ethylene oxide)-block-poly(L-lactide) triblock copolymers by liquid chromatography. Retention of liquid chromatography at the critical condition; Separation of mechanism of block copolymer.

Hybrid perovskites, as emerging multifunctional semiconductors, have demonstrated dual electronic/ionic conduction properties. We report a metal/ion interaction induced p-i-n junction across slightly n-type doped MAPbI 3 single crystals with Au/MAPbI 3 /Ag configuration based on interface dependent Seebeck effect, Hall effect and time-of-flight secondary ion mass spectrometry analysis. The organic cations (MA + ) interact with Au atoms, forming positively charged coordination complexes at Au/MAPbI 3 interface, whereas iodine anions (I - ) can react with Ag contacts, leading to interfacial ionic polarization. Such metal/ion interactions establish a p-doped region near the Au/MAPbI 3 interface due to the formation of MA + vacancies, and an n-doped region near the Ag/MAPbI 3 interface due to formation of I - vacancies, consequently forming a p-i-n junction across the crystal in Au/MAPbI 3 /Ag configuration. Therefore, the metal/ion interaction plays a role in determining the surface electronic structure and semiconducting properties of hybrid perovskites.

Polystyrene of different molecular weights and their binary mixtures are studied in terms of their various mechanical responses to uniaxial compression at different temperatures. PS of M w = 25 kg/mol is completely brittle until it is above its glass transition temperature T g . In contrast, upon incorporation of a high molecular weight component, PS mixtures turn from barely ductile a few degrees below its T g to ductile over 40° below T g . In the upper limit, a PS of M w = 319 kg/mol yields and undergoes plastic flow, even at T = -70 °C. The observed dependence of mechanical responses on molecular weight and molecular weight distribution can be adequately rationalized by the idea that yielding and plastic compression are caused by chain networking.

External electric fields align nanostructured block copolymers by either rotation of grains or nucleation and growth depending on how strongly the chemically distinct block copolymer components are segregated. In close vicinity to the order-disorder transition, theory and simulations suggest a third mechanism: selective disordering. We present a time-resolved small-angle X-ray scattering study that demonstrates how an electric field can indeed selectively disintegrate ill-aligned lamellae in a lyotropic block copolymer solution, while lamellae with interfaces oriented parallel to the applied field prevail. The present study adds an additional mechanism to the experimentally corroborated suite of mechanistic pathways, by which nanostructured block copolymers can align with an electric field. Our results further unveil the benefit of electric field assisted annealing for mitigating orientational disorder and topological defects in block copolymer mesophases, both in close vicinity to the order-disorder transition and well below it.

We have synthesized linear ABC triblock terpolymers containing poly(1,3-cyclohexadiene), PCHD, as an end block and characterized their morphologies in the melt. Specifically, we have studied terpolymers containing polystyrene (PS), polybutadiene (PB), and polyisoprene (PI) as the other blocks. Systematically varying the ratio of 1,2- /1,4-microstructures of poly(1,3-cyclohexadiene), we have studied the effects of conformational asymmetry among the three blocks on the morphologies using transmission electron microscopy (TEM), small-angle X-ray scattering (SAXS), and self-consistent field theory (SCFT) performed with PolySwift++. Our work reveals that the triblock terpolymer melts containing a high percentage of 1,2-microstructures in the PCHD block are disordered at 110 °C for all the samples, independent of sequence and volume fraction of the blocks. In contrast, the triblock terpolymer melts containing a high percentage of 1,4-microstructure form regular morphologies known from the literature. The accuracy of the SCFT calculations depends on calculating the χ parameters that quantify the repulsive interactions between different monomers. Simulations using χ values obtained from solubility parameters and group contribution methods are unable to reproduce the morphologies as seen in the experiments. However, SCFT calculations accounting for the enhancement of the χ parameter with an increase in the conformational asymmetry lead to an excellent agreement between theory and experiments. These results highlight the importance of conformational asymmetry in tuning the χ parameter and, in turn, morphologies in block copolymers.

The synthesis and characterization of well-defined polyacid based block copolymers containing polyisoprene (PI) are reported. The challenge of maintaining the integrity of the polydiene while producing polyacid from the tert -butyl ester precursor is addressed in this communication. A general purification method was also developed, taking advantage of the different polarities of each block. The polystyrene- b -polyisoprene- b -poly(acrylic acid) (PS- b -PI- b -PAA) triblock terpolymers form multicompartmental micelles via aqueous self-assembly. Our work reveals the morphological consequences of unique balances among global and local interactions.

In contrast to incompressible liquid solutions, compressible near-critical solutions of block copolymers allow for controlling rapid structure transformations with pressure alone. For example, when dissolved in near-critical propane, polystyrene-block-polybutadiene can form a random molecular solution at high pressures, a micellar solution at moderate pressures, and a solvent-free precipitate at low pressures. In contrast to the unstructured virgin copolymer, such a propane-treated precipitate rapidly self assembles toward structures characteristic of equilibrated block copolymers, such as lamellae, spheres or cylinders, which depend on the block ratio rather than on the decompression rate or temperature, at least within the rate and temperature ranges investigated in this work. At lower temperatures, however, say below 40 °C, glass transition of the styrene-butadiene diblocks can inhibit independent structure formation while crystallization of their hydrogenated-butadiene analogs can preserve the micellar-solution structure.

Poly(l-leucine) grafted hyaluronan (HA-g-PLeu) has been synthesized via a Michael addition reaction between primary amine terminated poly(l-leucine) and acrylate-functionalized HA (TBAHA-acrylate). The precursor hyaluronan was first functionalized with acrylate groups by reaction with acryloyl chloride in the presence of triethylamine in N,N-dimethylformamide. (1)H NMR analysis of the resulting product indicated that an increase in the concentration of acryloylchoride with respect to hydroxyl groups on HA has only a moderate effect on functionalization efficiency, f. A precise control of stoichiometry was not achieved, which could be attributed to partial solubility of intermolecular aggregates and the hygroscopic nature of HA. Michael addition at high [PLeu-NH(2)]/[acrylate](TBAHA) ratios gave a molar grafting ratio of only 0.20 with respect to the repeat unit of HA, indicating grafting limitation due to insolubility of the grafted HA-g-PLeu. Soluble HA-g-PLeu graft copolymers were obtained for low grafting ratios (<0.039) with <8.6% by mass of PLeu and were characterized thoroughly using light scattering, (1)H NMR, FT-IR, and AFM techniques. Light scattering experiments showed a strong hydrophobic interaction between PLeu chains, resulting in aggregates with segregated nongrafted HA segments. This yields local networks of aggregates, as demonstrated by atomic force microscopy. Circular dichroism spectroscopy showed a β-sheet conformation for aggregates of poly(l-leucine).

This study investigates the structures of layers of amphiphilic diblock copolymers of poly(t-butyl styrene)-poly(styrene sulfonate) (PtBS-PSS) adsorbed on both the bare mica surface (hydrophilic) and an octadecyltriethoxysilane (OTE)-modified mica surface (hydrophobic). When the surface is rendered hydrophobic, the nonsoluble block exhibits stronger interaction with the surface and higher adsorbed masses are achieved. Interaction forces between two such adsorbed layers on both substrates were measured using the surface forces apparatus. The effect of salt concentration (Cs) and molecular weight (N) on the height of the self-assembled layers (L0) was examined in each case. The resulting scaling relationship is in good agreement with predictions of the brush model, L0 proportional to N(1.0) in the low-salt limit and L0N(-1) proportional to (Cs/sigma)(-0.32) in the salted regime, when adsorption takes place onto the hydrophobized mica surface. For adsorption on the bare mica surface, L0N(-0.7) proportional, variant Cs(-0.17) agrees with the scaling prediction of the sparse tethering model. The results suggest that, on the hydrophilic bare mica surface, the adsorbed amount is not high enough to form a brush structure and only very little intermolecular stretching of the tethered chains occurs; in contrast, the presence of the hydrophobic OTE layer increases the tethering density such that the polyelectrolyte chains adopt a brush conformation.